Biomineralization provides load-bearing and protective functions to living organisms by reinforcing soft tissues. Translation of biomineralization principles to materials science in a controlled and self-organized fashion is highly desirable but challenging. A major lesson from natural systems is that crystallization may be controlled by compartmentalization and templating. Here, we develop a crystallization technique based on graphene oxide-mediated compartmentalization and on templating prismatic growth of calcite nanocoatings via control of ionic diffusivity into the microcompartments, which results in a multistage, self-organized crystallization and represents an effective strategy for providing continuous nanocoatings and enhancing the tribological performance of polymeric surfaces under contact stresses. The present research offers a bottom-up approach of using very basic biomineralization principles for the protection of polymeric surfaces, which are of interest for biomedical applications and the fabrication of high-performance functional materials in a sustainable manner.

The controllable integration of low-dimensional nanomaterials on solid surfaces is pivotal for the fabrication of next-generation miniaturized electronic and optoelectronic devices. For instance, organization of two-dimensional (2D) nanomaterials on polymeric surfaces paves the way for the development of flexible electronics for applications in wearable devices. Nevertheless, the understanding of the molecular interactions between these nanomaterials and the polymeric surfaces remains limited, which impedes the rational design of 2D nanomaterial-based functional coatings. In the current work, we report that graphene oxide (GO) nanosheets, in their dispersion phase, can be adsorbed on multiple polymeric surfaces in a spontaneous manner. Both experimental findings and simulational results indicate that the main driving force is hydrogen bonding interactions, although other molecular interactions such as polarity and dispersion ones contribute to the adsorption as well. The relatively high hydrogen bonding interactions cause not only increased GO surface coverage but also enhanced GO adsorption kinetics on polymeric surfaces. The adsorbed GO layers are robust, which can be explained by the large aspect ratios of GO nanosheets and the presence of multiple spots for molecular interactions. As a proof of concept, GO-covered polymethyl methacrylate effectively decreases surface static charges when compared with its pristine counterpart. The integration of the GO constituents turns many inert polymeric substrates into multifunctional hybrids, and the functional groups on GO can be used further to bridge with additional functional materials for the development of high-performance electronic devices.

Gel-mediated crystallization is a common system to produce self-organized materials, which is fundamental to the development of bottom-up approaches to functional complex materials. Mineralization in hydrogel matrices nevertheless remains empirical in the generation of crystallization products with tailored heterogeneous structures. We demonstrate that the employment of the hydrogels with proper cationic diffusivity can trigger the consecutive growth of oriented, granular-rhombohedral heterogeneous structures. The controllable morphogenesis leads to continuous calcitic CaCO3 films comprising spatial heterogeneity, where epitaxial match assumedly favors the successive deposition of both granular and rhombohedral layers. The scenario of consecutive growth is disclosed, where the thickness of the granular layers can become a valuable indicator to reflect the retardancy degree of crystallization. The evaluation of the physicochemical properties of the hydrogels finally establishes a direct correlation between the cationic diffusivity of the hydrogels and the appearance of the heterogeneous structures. The current work therefore sheds light on the implementation of rational morphogenetic approaches to crystalline materials with tailored complex architectures.